Electronic device

ABSTRACT

Electronic devices, such as organic thin film transistors, with improved mobility are disclosed. The semiconducting layer comprises layers or striations of an organic semiconductor and graphene, including alternating layers/striations of such materials. The organic semiconductor and graphene layers interact well together because both materials form lamellar sheets. The presence of graphene enhances mobility by correcting molecular packing defects in the organic semiconductor layers, and the conductivity of graphene can be controlled. Finally, both materials are flexible, allowing for flexible semiconductor layers and transistors.

BACKGROUND

The present disclosure relates, in various embodiments, to compositionssuitable for use in electronic devices, such as thin film transistors(“TFT”s), with improved performance characteristics, such as improvedmobility. The compositions are used to form semiconducting layers thatinclude an organic semiconductor and graphene.

Thin film transistors (TFTs) are fundamental components in modern-ageelectronics, including, for example, sensors, image scanners, memorydevices, radio frequency identification tags, and electronic displaydevices. It is usually desired to make TFTs which have not only muchlower manufacturing costs, but also appealing mechanical properties suchas being physically compact, lightweight, flexible, and having enhancedperformance characteristics. Organic thin film transistors (OTFTs)promise the above desired benefits.

OTFTs are generally composed of a supporting substrate, threeelectrically conductive electrodes (gate, source and drain electrodes),a channel semiconducting layer, and an electrically insulating gatedielectric layer separating the gate electrode from the semiconductinglayer.

It is desirable to improve the performance of known OTFTs. One measureof performance is the charge carrier mobility of the semiconductinglayer. The mobility is measured in units of cm²/V·sec, higher mobilityis desired. Although the last two decades have seen significant increasein mobility for printable organic semiconductors such as polythiophenesand polythiophene derivatives, the mobility values level off at around0.1-0.2 cm²/V·sec, which limits the applications of OTFTs. Therefore,there is a need to develop new technologies to dramatically improve themobility for broad applications.

BRIEF DESCRIPTION

The present disclosure is directed, in various embodiments, toelectronic devices, such as a thin film transistor, with a dielectriclayer and a semiconducting layer that provides improved performance. Thesemiconducting layer includes organic semiconductor/graphene compositematerials. For example, in several embodiments, the semiconducting layerincludes layers or striations of an organic semiconductor and graphene.In some embodiments, the semiconducting layer comprises alternatinglayers or striations of (i) an organic semiconductor; and (ii) graphene.In other embodiments, the semiconducting layer comprises graphene whichis dispersed substantially throughout the semiconducting layer.

Disclosed in further embodiments is an electronic device comprising asemiconducting layer; the semiconducting layer comprising an organicsemiconductor and graphene. The organic semiconductor and graphene maybe organized into layers or striations. The organic semiconductorlayers/striations may alternate with the graphene layers/striations, orthey may be stratified with respect to each other.

The graphene can also be chemically modified. In embodiments, thegraphene is modified with a conjugated group selected from the groupconsisting of thiophene-based oligomers and polymers, pyrenes,phthalocyanines, polyphenylvinylidenes, polyfluorenes, polycarbazoles,polyindolocarbazoles, polytriarylamines, and polyphenylenes.

The organic semiconductor may be a polythiophene of Formula (I):

wherein A is a divalent linkage; each R is independently selected fromhydrogen, alkyl or substituted alkyl, aryl or substituted aryl, alkoxyor substituted alkoxy, a heteroatom-containing group, or halogen; and nis from 2 to about 5,000.

The divalent linkage can be selected from

and combinations thereof, wherein each R′ is independently selected fromhydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,halogen, —CN, or —NO₂.

In particular versions, the organic semiconductor is a polythiophene ofFormula (II), (III), (IV), (V), (VI), (VII), or (VIII):

wherein each R, R′, and R₁ is independently selected from hydrogen,alkyl or substituted alkyl, aryl or substituted aryl, alkoxy orsubstituted alkoxy, a heteroatom-containing group, or halogen; and n isfrom 2 to about 5,000.

Each graphene layer or striation may have functional sites, such ascarbonyl groups, carboxylic acid groups, epoxide groups, or hydroxylgroups. The semiconducting layer may comprise from about 0.001 to about10 percent by weight of the graphene, including from about 0.01 to about5 weight percent graphene. The graphene layer may further comprisegraphite oxide.

A graphene layer/striation can be made by depositing graphite oxide andreducing the graphite oxide to form the graphene layer/striation.

Alternatively, a graphene layer/striation can be made by dispersinggraphite oxide in an aqueous solution comprising water and ammonia;converting the graphite oxide to graphene; dispersing the aqueoussolution in an aprotic solvent and neutralizing any static charge;dispersing the graphene in an organic solvent; and depositing theorganic solvent on a surface to form a graphene layer.

The semiconducting layer could also be made by forming a homogeneoussuspension of the organic semiconductor and graphene oxide; depositingthe suspension on a surface; and converting the graphene oxide tographene.

Alternatively, the semiconductor layer could be made by a processcomprising: heating the graphite to form graphene; dispersing thegraphene into a graphene dispersion; mixing the graphene dispersion withan organic semiconductor to form a mixture; and depositing the mixtureon a surface of a substrate to form the semiconducting layer.

Alternatively, the semiconducting layer could be made by a processcomprising: dispersing graphite oxide in an aqueous solution comprisingwater and ammonia; converting the graphite oxide to graphene; dispersingthe aqueous solution in an aprotic solvent and neutralizing any staticcharge; dispersing the graphene in an organic solvent to form a graphenedispersion; mixing the graphene dispersion with an organic semiconductorto form a mixture; and depositing the mixture on a surface of asubstrate to form the semiconducting layer.

Disclosed in other embodiments is an electronic device comprising asemiconducting layer; the semiconducting layer comprising a first layerand a second layer; the first layer comprising an organic semiconductor;and the second layer comprising graphene. The organic semiconductor maycomprise a majority of the first layer, and the graphene may comprise amajority of the second layer.

In embodiments, the first layer does not contain graphene. In otherembodiments, the second layer does not contain an organic semiconductor.

The electronic device may further comprise a third layer, the thirdlayer comprising an organic semiconductor; the second layer beinglocated between the first layer and the third layer.

Also disclosed in embodiments is an electronic device comprising asemiconducting layer, the semiconducting layer comprising an organicsemiconductor and graphene. The organic semiconductor and graphene maybe stratified with respect to each other.

Also disclosed in embodiments is an electronic device comprising asemiconducting layer, the semiconducting layer comprising an organicsemiconductor and graphene. The graphene is dispersed substantiallythroughout the semiconducting layer.

The graphene can form a percolation network within the semiconductorsemiconducting layer. The graphene concentration in the semiconductinglayer can be lower than the critical concentration for a percolationnetwork.

Also disclosed is a process for forming a semiconducting layer on asubstrate, comprising forming at least one organic semiconductor layerand at least one graphene layer upon a substrate.

The graphene layer may be formed by depositing graphite oxide andreducing the graphite oxide to form the graphene layer.

The organic semiconductor layer and the graphene layer could also beself-assembled by: dispersing graphite oxide in an aqueous solutioncomprising water and ammonia; converting the graphite oxide to graphene;dispersing the aqueous solution in an aprotic solvent and neutralizingany static charge; dispersing the graphene in an organic solvent to forma graphene dispersion; mixing the graphene dispersion with an organicsemiconductor to form a mixture; and depositing the mixture upon thesubstrate to form at least one organic semiconductor layer and at leastone graphene layer.

The organic semiconductor layer and the graphene layer could also beformed by forming a homogeneous suspension of the organic semiconductorand graphene oxide; converting the graphene oxide to graphene; anddepositing the suspension on a surface of the substrate to form at leastone organic semiconductor layer and at least one graphene layer.

These and other non-limiting characteristics of the exemplaryembodiments of the present disclosure are more particularly describedbelow.

BRIEF DESCRIPTION OF THE DRAWINGS

The following is a brief description of the drawings, which arepresented for the purpose of illustrating the exemplary embodimentsdisclosed herein and not for the purpose of limiting the same.

FIG. 1 is an exemplary embodiment of an OTFT of the present disclosure.

FIG. 2 is a second exemplary embodiment of an OTFT of the presentdisclosure.

FIG. 3 is a third exemplary embodiment of an OTFT of the presentdisclosure.

FIG. 4 is a fourth exemplary embodiment of an OTFT of the presentdisclosure.

FIG. 5 is an exploded view of a semiconducting layer.

FIG. 6 is a top view of an organic semiconductor-containing layer in thesemiconducting layer of the present disclosure.

FIG. 7 is a top view of a graphene-containing layer in thesemiconducting layer of the present disclosure.

FIG. 8 is an illustration of slowed charge transfer in a semiconductinglayer lacking graphene.

FIG. 9 is an illustration of charge transfer in a semiconducting layercontaining graphene.

FIG. 10 is an illustration of a semiconducting layer having striationsof organic semiconductor and graphene.

DETAILED DESCRIPTION

A more complete understanding of the components, processes, and devicesdisclosed herein can be obtained by reference to the accompanyingfigures. These figures are merely schematic representations based onconvenience and the ease of demonstrating the present development andare, therefore, not intended to indicate relative size and dimensions ofthe devices or components thereof and/or to define or limit the scope ofthe exemplary embodiments.

Although specific terms are used in the following description for thesake of clarity, these terms are intended to refer only to theparticular structure of the embodiments selected for illustration in thedrawings and are not intended to define or limit the scope of thedisclosure. In the drawings and the following description below, it isto be understood that like numeric designations refer to components oflike function.

FIG. 1 illustrates a first organic thin film transistor (OTFT)embodiment or configuration. The OTFT 10 comprises a substrate 20 incontact with the gate electrode 30 and a dielectric layer 40. Althoughhere the gate electrode 30 is depicted within the substrate 20, this isnot required. However, of some importance is that the dielectric layer40 separates the gate electrode 30 from the source electrode 50, drainelectrode 60, and the semiconducting layer 70. The source electrode 50contacts the semiconducting layer 70. The drain electrode 60 alsocontacts the semiconducting layer 70. The semiconducting layer 70 runsover and between the source and drain electrodes 50 and 60. An optionalinterfacial layer 80 is located between dielectric layer 40 andsemiconducting layer 70.

FIG. 2 illustrates a second OTFT embodiment or configuration. The OTFT10 comprises a substrate 20 in contact with the gate electrode 30 and adielectric layer 40. The semiconducting layer 70 is placed over or ontop of the dielectric layer 40 and separates it from the source anddrain electrodes 50 and 60. Optional interfacial layer 80 is locatedbetween dielectric layer 40 and semiconducting layer 70.

FIG. 3 illustrates a third OTFT embodiment or configuration. The OTFT 10comprises a substrate 20 which also acts as the gate electrode and is incontact with a dielectric layer 40. The semiconducting layer 70 isplaced over or on top of the dielectric layer 40 and separates it fromthe source and drain electrodes 50 and 60. Optional interfacial layer 80is located between dielectric layer 40 and semiconducting layer 70.

FIG. 4 illustrates a fourth OTFT embodiment or configuration. The OTFT10 comprises a substrate 20 in contact with the source electrode 50,drain electrode 60, and the semiconducting layer 70. The semiconductinglayer 70 runs over and between the source and drain electrodes 50 and60. The dielectric layer 40 is on top of the semiconducting layer 70.The gate electrode 30 is on top of the dielectric layer 40 and does notcontact the semiconducting layer 70. Optional interfacial layer 80 islocated between dielectric layer 40 and semiconducting layer 70.

In embodiments, the semiconducting layer contains an organicsemiconductor and graphene. The organic semiconductor and grapheneself-assemble so that the semiconducting layer is stratified, i.e. theorganic semiconductor and graphene are in different portions of thesemiconducting layer.

In other embodiments, the semiconducting layer is formed from one ormore series of sublayers, i.e. layered structures. For example, theremay be two alternating sets of sublayers. The first set of sublayers isformed from an organic semiconductor. The second set of sublayers isformed from graphene. Put another way, in certain structures, theorganic semiconductor layers and graphene layers are arranged in analternating pattern. The term “alternating” refers to the fact that atleast one graphene layer is between two organic semiconductor layers andthat at least one organic semiconductor layer is between two graphenelayers. For example, where A denotes an organic semiconductor layer andB denotes a graphene layer, an -A-B-A-B-A-pattern, an-A-A-B-B-A-A-B-B-A-A- pattern, and an -A-B-B-A-B-A-B-B-A- pattern wouldall be considering alternating sets or alternating patterns of the twosets of sublayers.

In other embodiments, the semiconducting layer comprises a first layer,a second layer, and optionally a third layer. The second layer isbetween the first and third layers. The first layer and third layercomprise the organic semiconductor, and the second layer comprisesgraphene. In some embodiments, the second layer directly contacts thetwo layers, i.e. is adjacent to both the first and third layers, i.e. inan -A-B-A-B-A pattern.

The arrangement of these layers can be seen in FIG. 5. Organicsemiconductor layers 100 and graphene layers 110 are shown in anexploded view of the semiconducting layer 70.

FIG. 6 is a top view of the organic semiconductor layer 100. FIG. 7 is atop view of the graphene layer 110. Depicted in graphene layer 110 aretwo types of graphene plates 112 and 114. Graphene plate 112 representspure graphene, while graphene plate 114 represents graphene that isformed by the reduction of graphite oxide and has oxygen-containingfunctional sites.

As mentioned, the organic semiconductor and graphene are in differentportions of the semiconducting layer. It should be understood that theorganic semiconductor/graphene do not need to make up the entirety ofthe layers/sublayers they are in. For example, as seen in FIG. 10, thesemiconducting layer 200 has layers/striations of organic semiconductorand graphene. Portions of sublayer 210 contain graphene 212, while otherportions of that sublayer contain organic semiconductor 214. Thoseportions or domains of different materials in each sublayer may not beevenly distributed between sublayers, as seen in the difference betweensublayers 210, 220, and 230. However, in additional versions, the layersof the semiconducting layer that contain the organic semiconductor donot contain graphene, and the layers of the semiconducting layer thatcontain graphene do not contain the organic semiconductor. In additionalversions, the organic semiconductor layers consist of the organicsemiconductor, and/or the graphene layers consist of graphene.

The organic semiconductor is typically a majority of the overallsemiconducting layer. Similarly, the organic semiconductor is generallya majority of each organic semiconductor layer, and the graphene isgenerally a majority of each graphene layer. The term “majority” meansgreater than 50 weight percent of the relevant layer, including fromabout 55 to about 99 weight percent, or in further embodiments fromabout 70 to about 95 weight percent.

In some embodiments, the organic semiconductor is a p-type organicsemiconductor. In some embodiments, the organic semiconductor is ann-type semiconductor. In other embodiments, the organic semiconductor isan ambipolar semiconductor (both p and n-types).

In some embodiments, the organic semiconductor is a small molecularcompound. Exemplary small molecular compounds include pentacene andpentacene derivatives (pentacene precursors and pentacene analogs),oligothiophenes, phthalocyanines, naphthalene-bisimides, and otherfused-ring aromatic compounds.

The organic semiconductor may be, in some embodiments, an organicsemiconducting polymer. In some embodiments, the organic semiconductorused in the semiconducting layer is a polythiophene of Formula (I):

wherein A is a divalent linkage; each R is independently selected fromhydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkoxy orsubstituted alkoxy, a heteroatom-containing group, halogen, —CN, or—NO₂; and n is from 2 to about 5,000. In some embodiments, R is nothydrogen.

The term “alkyl” refers to a radical composed entirely of carbon atomsand hydrogen atoms which is fully saturated and of the formulaC_(n)H_(2n+)1. The term “aryl” refers to an aromatic radical composedentirely of carbon atoms and hydrogen atoms. The term “alkoxy” refers toan alkyl radical which is attached to an oxygen atom.

The substituted alkyl, substituted aryl, and substituted alkoxy groupscan be substituted with, for example, alkyl, halogen, —CN, and —NO₂. Anexemplary substituted alkyl group is a perhaloalkyl group, wherein oneor more hydrogen atoms in an alkyl group are replaced with halogenatoms, such as fluorine, chlorine, iodine, and bromine. The term“heteroatom-containing group” refers to a radical which is originallycomposed of carbon atoms and hydrogen atoms that forms a linearbackbone, a branched backbone, or a cyclic backbone. This originalradical is saturated or unsaturated. One or more of the carbon atoms inthe backbone is then replaced by a heteroatom, generally nitrogen,oxygen, or sulfur, to obtain a heteroatom-containing group. The term“heteroaryl” refers generally to an aromatic compound containing atleast one heteroatom replacing a carbon atom, and may be considered asubset of heteroatom-containing groups.

In particular embodiments, both R groups are alkyl having from about 6to about 18 carbon atoms. In certain desirable examples, both R groupsare the same. In further desired embodiments, both R groups are alkyl,particularly —C₁₂H₂₅.

The divalent linkage A forms a single bond to each of the two thienylmoieties in Formula (I). Exemplary divalent linkages A include:

and combinations thereof, wherein each R′ is independently selected fromhydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkoxy orsubstituted alkoxy, a heteroatom-containing group, halogen, —CN, or—NO₂. It should be noted that the divalent linkage A will always bedifferent from the two thiophene monomers shown in Formula (I); in otherwords, Formula (I) will not reduce to being a polythiophene made fromonly one monomer.

In particular embodiments, the organic semiconductor is a polythiopheneof Formula (II), (III), (IV), (V), (VI), or (VII):

wherein each R and R′ is independently selected from hydrogen, alkyl orsubstituted alkyl, aryl or substituted aryl, alkoxy or substitutedalkoxy, a heteroatom-containing group, or halogen; and n is an integerfrom about 2 to about 5,000. In particular embodiments, thepolythiophene is of Formula (II) and each R is alkyl.

In other embodiments, the organic semiconductor is a polythiophene ofFormula (VIII):

wherein R₁ is selected from hydrogen, alkyl or substituted alkyl, arylor substituted aryl, alkoxy or substituted alkoxy, aheteroatom-containing group, or halogen; and n is an integer from about2 to about 5,000.

When R or R′ are alkyl, alkoxy, aryl, or their substituted derivativesthereof, they may contain from 1 to about 35 carbon atoms, or from about1 to about 30 carbon atoms, or from about 1 to about 20 carbon atoms, orfrom about 6 to about 18 carbon atoms, inclusive of any side-chains. Thevariable n represents the number of repeating units, and may be a numberfrom about 2 to about 5,000, about 2 to about 2,500, about 2 to about1,000, about 100 to about 800, or from about 2 to about 100.

In specific embodiments, each R is independently an alkyl side-chaincontaining from about 6 to about 30 carbon atoms, and each R isindependently selected an alkyl side-chain containing from 1 to about 5carbon atoms. In other embodiments, each R is independently selected analkyl side-chain containing from 0 to about 5 carbon atoms, and each R′is an alkyl side-chain containing from 6 to about 30 carbon atoms. Instill other embodiments, R and R′ are independently alkyl with about 1to about 35 carbon atoms, or arylalkyl with about 7 to about 42 carbonatoms. Exemplary alkyl groups include methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Exemplaryarylalkyl groups include methylphenyl(tolyl), ethylphenyl, propylphenyl,butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl,nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl,tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl,and octadecylphenyl. In particular embodiments, R and R′ are representalkyl or substituted alkyl groups having from about 1 to about 35 carbonatoms.

In a specific embodiment, the R groups are identical to each other; andthe R′ groups are identical to each other. In other embodiments, the Rand R′ groups are identical to each other. In another specificembodiment, the R and R′ substituents are identical alkyl groups havingfrom about 6 to about 18 carbon atoms.

When the organic semiconductor is a polymer, it may have a weightaverage molecular weight of from about 1,000 to about 1,000,000, or fromabout 5000 to about 100,000.

The graphene layers in the semiconducting layer comprise graphene.Ideally, the term graphene refers to a one-atom-thick sheet ofsp²-bonded carbon atoms arranged in a honeycomb pattern, i.e. hexagonalcells. Graphene can also be considered a polycyclic aromatichydrocarbon. The term “graphene” should not be considered as referringonly to the hexagonal cell structure made exclusively of carbon atoms.For example, it is contemplated that certain substituents/functionalgroups may be attached to the hexagonal cells, as described furtherherein, or that precursors such as graphene oxide may also be present.In embodiments, the graphene is dispersed substantially throughout thesemiconducting layer, i.e. throughout the length, width, and thicknessof the semiconducting layer.

In some embodiments, a graphene layer may be a few sheets (e.g. fromabout 1 to about 10 or from about 1 to about 3 sheets) of sp²-bondedcarbon atoms arranged in a honeycomb pattern. In some embodiments, thegraphene layers further comprise graphene oxide. Graphene oxide andgraphite oxide both refer to a precursor of graphene.

Each graphene layer can be formed as one continuous sheet, or can bemade up of several small sheets or plates of graphene. Several methodsof making graphene are known. In particular, methods where graphene isformed from the reduction of graphite oxide are especially suitable forthis application. One large advantage of using graphite oxide is thatgraphite oxide itself is easier to handle than graphene. For example,graphite oxide is easily dispersed in a solvent for liquid depositionprocesses. Also, graphite oxide itself is less conductive than graphene,so the overall conductivity of the graphene layer can be controlled bychanging the ratio between graphite oxide and graphene by controllingthe degree of reduction of the graphite oxide.

The resulting semiconducting layer will have increased mobility comparedto a semiconducting layer lacking graphene. Without being bound bytheory, it appears that certain synergistic effects result from thecombination of an organic semiconductor with graphene. First, organicsemiconductors, such as polythiophenes, often form large lamellarsheets, which further stack together and form pi-pi stacking arrays.Those lamellar sheets can be considered as two-dimensionalone-atom-thick layers. Graphene also forms such layers, allowing thegraphene layers to participate in the pi-pi stacking arrays. Anillustrative diagram of such stacking is shown in FIG. 5, as describedabove. This structural similarity allows the graphene to enhance thepi-pi stacking of the organic semiconductor, such that a homogeneousorganic semiconductor/graphene composite is expected. In contrast,carbon nanotubes have a rod-like structure which can disturb the packingof the organic semiconductor.

As a result of the compatible planar stacking between the organicsemiconductor and the graphene, mobility can be increased in twoaspects. Graphene can form a percolation network or near percolationnetwork to improve apparent mobility by reducing the effective channellength. A percolation network is a connected structure that spans anon-minimal linear dimension of the entire semiconducting layer. Herein,a non-minimal linear dimension is a linear dimension of the layer thatis not the layer's smallest linear dimension; in many cases, the layerthickness is the minimal dimension of the layer. The criticalconcentration for a percolation network, or percolation threshold, canbe determined for example by measuring the conductance of a layer.Before the formation of a percolation network, the conductance of thelayer is dominated by the conductance of the organic semiconductor. Whenthe percolation network is formed, the conductance of the semiconductinglayer is dominated by the graphene. Given the conductance differencebetween the graphene and the organic semiconductor, the percolationthreshold can be determined. In embodiments, the concentration ofgraphene in the semiconducting layer is less than the criticalconcentration for a percolation network. It is should be noted that thepercolation threshold will vary depending on the composition of thesemiconducting layer. When a different organic semiconductor is used, adifferent percolation threshold may be observed. At concentrations belowthe percolation threshold, the graphene does not form a conducting orsemiconducting network that could short-circuit the organicsemiconductor matrix.

More important, since the graphene sheets participate in the pi-pistacking of the organic semiconductor, it can dramatically increase theinter-layer charge transfer mobility. For example, the presence of thegraphene layers allow for correction of any defects in the pi-pistacking array from the organic semiconductor by providing additionalpaths for charge transfer. For example, as shown in FIG. 8, thesemiconducting layer contains lamellar layers 100 formed from theorganic semiconductor, but lacking graphene. A defect 122 (representedby a circle) in an organic semiconductor layer 116 significantly slowsdown the charge transfer (represented by arrow 120) through thesemiconducting layer because the current can only flow through thestacked aromatic thienyl groups and not through the R groups(represented by arrow 124). However, if graphene layers 110 areincorporated as in FIG. 9, they provide a path for interlayer transfer,allowing electrons or holes to pass around the defect, as represented byarrows 120, 124, 126, 128, 130.

Second, the conductivity of the graphene layers can be controlled fromhighly conductive to semiconductive depending on the method by which thegraphene layer is formed. For example, one method of forming a graphenelayer occurs by depositing graphite oxide, then reducing the graphiteoxide to graphene through the application of heat. Graphite oxide isless conductive than graphene, so the ratio of graphene to graphiteoxide changes the conductivity of the graphene layer, and that ratio iseasily controlled by varying the amount of heat applied. In contrast,carbon nanotubes are always a mixture of conductive and semiconductivenanotubes, so that the conductivity cannot be easily controlled.

Additionally, the graphene and the organic semiconductor are both veryflexible, allowing flexible electronic devices to be made. Graphene isalso cost-effective when compared to carbon nanotubes.

Graphene sheets or plates generally can be modified to create functionalsites on various carbon atoms, both on the edges of the sheet/plate andon internal carbon atoms as well. For example, it is known that graphenecan be treated to obtain oxygen-containing functional groups such ascarbonyl, carboxylic acid, epoxide, and hydroxyl groups at functionalsites. In some embodiments, these functional groups are modified bygrafting other moieties to the graphene sheet. As another example, thegraphene can be chemically modified with a conjugated group selectedfrom the group consisting of thiophene-based oligomers and polymers,pyrenes, phthalocyanines, polyphenylvinylidenes, polyfluorenes,polycarbazoles, polyindolocarbazoles, polytriarylamines, andpolyphenylenes.

The semiconducting layer can be made in several different ways. Forexample, one approach is to briefly heat graphite (e.g. to a temperatureof 1000° C., including from about 850° C. to about 1200° C.) in aforming gas, such as 3% hydrogen in argon, to exfoliate the graphite andobtain graphene. The graphene can be dispersed in a solvent along withthe organic semiconductor and sonicated to obtain a homogeneousdispersion. The dispersion is then deposited upon a substrate and driedto form the semiconducting layer.

Another approach to forming the semiconducting layer is to dispersegraphite oxide in a mixture of water (i.e. aqueous solution) and ammonia(NH₃) by simple sonication. This results in a stable dispersion due toelectrostatic stabilization. See Nature Nanotechnology, 2008, vol. 3,pp. 101-105). The graphite oxide can then be converted to graphene byreduction. The aqueous graphene dispersion can be stabilized with asurfactant which is already present or is added after conversion tographene. The graphene can then be re-dispersed in an aprotic solvent,such as DMF acetone, THF, acetate, ether, and the like. Afterneutralizing any remaining static charge, the hydrophobic graphene canbe re-dispersed in a common organic solvent, such as toluene,chlorobenzene, dichlorobenzene, xylene, mesitylene, chloroethane,chloromethane, and the like and deposited on a substrate. This approachforms a graphene layer. The organic semiconductor layer can be depositedvia a different solution comprising the organic semiconductor and asolvent.

Another approach is to disperse graphite oxide and the organicsemiconductor together in a solvent to form a deposition solution. Thetwo components are then deposited to form a thin film. The graphiteoxide can then be reduced to graphene in situ, for example by exposureto hydrazine vapor and mild heating simultaneously. Alternatively,graphene can be formed as described above and then dispersed in anorganic solvent to form a graphene dispersion. This dispersion is thenmixed with an organic semiconductor to form a mixture. The mixture isthen deposited on a substrate to form the semiconducting layer.

It should be noted that when the graphene and organic semiconductor aresimultaneously deposited, they can self-assemble to form separate layersdue to their different structures. The R groups of the organicsemiconductor, such as in the polythiophenes of Formulas (I) and (II),pack well together, while the graphene sheets/plates pack well together.

If desired, the semiconducting layer may comprise other organicsemiconductor materials. However, it is generally contemplated that thesemiconducting layer is formed solely with the organicsemiconductor/graphene layers. Alternatively, the semiconducting layercan be considered a composite. The graphene layers can comprise fromabout 0.001 to about 10 weight percent of the semiconducting layer,including from about 0.01 to about 5 weight percent. In other versions,the organic semiconductor layers comprise from about 90 to about 99.999weight percent of the semiconducting layer.

The semiconducting layer is from about 5 nm to about 1000 nm thick,especially from about 10 nm to about 100 nm thick. The semiconductinglayer can be formed by any suitable method. However, the semiconductinglayer is generally formed from a liquid composition(s), such as adispersion or solution, and then deposited onto a substrate of thetransistor. Exemplary deposition methods include liquid deposition suchas spin coating, dip coating, blade coating, rod coating, screenprinting, offset printing, stamping, ink jet printing, and the like, andother conventional processes known in the art.

The semiconducting layer of the present disclosure, comprising graphene,can be used in electronic devices. Exemplary electronic devices includethin film transistors, photovoltaic cells, sensors, memory, and lightemitting diodes.

The substrate may be composed of materials including but not limited tosilicon, glass plate, plastic film or sheet. For structurally flexibledevices, plastic substrate, such as for example polyester,polycarbonate, polyimide sheets and the like may be used. The thicknessof the substrate may be from about 10 micrometers to over 10 millimeterswith an exemplary thickness being from about 50 micrometers to about 5millimeters, especially for a flexible plastic substrate and from about0.5 to about 10 millimeters for a rigid substrate such as glass orsilicon.

The gate electrode is composed of an electrically conductive material.It can be a thin metal film, a conducting polymer film, a conductingfilm made from conducting ink or paste or the substrate itself, forexample heavily doped silicon. Examples of gate electrode materialsinclude but are not restricted to aluminum, gold, silver, chromium,indium tin oxide, conductive polymers such as polystyrenesulfonate-doped poly(3,4-ethylenedioxythiophene) (PSS-PEDOT), andconducting ink/paste comprised of carbon black/graphite or silvercolloids. The gate electrode can be prepared by vacuum evaporation,sputtering of metals or conductive metal oxides, conventionallithography and etching, chemical vapor deposition, spin coating,casting or printing, or other deposition processes. The thickness of thegate electrode ranges from about 10 to about 500 nanometers for metalfilms and from about 0.5 to about 10 micrometers for conductivepolymers.

The dielectric layer generally can be an inorganic material film, anorganic polymer film, or an organic-inorganic composite film. Examplesof inorganic materials suitable as the dielectric layer include siliconoxide, silicon nitride, aluminum oxide, barium titanate, bariumzirconium titanate and the like. Examples of suitable organic polymersinclude polyesters, polycarbonates, poly(vinyl phenol), polyimides,polystyrene, polymethacrylates, polyacrylates, epoxy resin and the like.The thickness of the dielectric layer depends on the dielectric constantof the material used and can be, for example, from about 10 nanometersto about 500 nanometers. The dielectric layer may have a conductivitythat is, for example, less than about 10⁻¹² Siemens per centimeter(S/cm). The dielectric layer is formed using conventional processesknown in the art, including those processes described in forming thegate electrode.

If desired, an interfacial layer may be placed between the dielectriclayer and the semiconducting layer. As charge transport in an organicthin film transistor occurs at the interface of these two layers, theinterfacial layer may influence the TFT's properties. Exemplaryinterfacial layers may be formed from silanes, such as those describedin U.S. patent application Ser. No. 12/101,942, filed Apr. 11, 2008.

Typical materials suitable for use as source and drain electrodesinclude those of the gate electrode materials such as gold, silver,nickel, aluminum, platinum, conducting polymers, and conducting inks. Inspecific embodiments, the electrode materials provide low contactresistance to the semiconductor. Typical thicknesses are about, forexample, from about 40 nanometers to about 1 micrometer with a morespecific thickness being about 100 to about 400 nanometers. The OTFTdevices of the present disclosure contain a semiconductor channel. Thesemiconductor channel width may be, for example, from about 5micrometers to about 5 millimeters with a specific channel width beingabout 100 micrometers to about 1 millimeter. The semiconductor channellength may be, for example, from about 1 micrometer to about 1millimeter with a more specific channel length being from about 5micrometers to about 100 micrometers.

The source electrode is grounded and a bias voltage of, for example,about 0 volt to about 80 volts is applied to the drain electrode tocollect the charge carriers transported across the semiconductor channelwhen a voltage of, for example, about +10 volts to about −80 volts isapplied to the gate electrode. The electrodes may be formed or depositedusing conventional processes known in the art.

If desired, a barrier layer may also be deposited on top of the TFT toprotect it from environmental conditions, such as light, oxygen andmoisture, etc. which can degrade its electrical properties. Such barrierlayers are known in the art and may simply consist of polymers.

The various components of the OTFT may be deposited upon the substratein any order, as is seen in the Figures. The term “upon the substrate”should not be construed as requiring that each component directlycontact the substrate. The term should be construed as describing thelocation of a component relative to the substrate. Generally, however,the gate electrode and the semiconducting layer should both be incontact with the dielectric layer. In addition, the source and drainelectrodes should both be in contact with the semiconducting layer. Theorganic semiconductor formed by the methods of the present disclosuremay be deposited onto any appropriate component of an organic thin-filmtransistor to form a semiconducting layer of that transistor.

The resulting transistor may have, in embodiments, a mobility of 0.2cm²/V·sec or greater.

The following examples illustrate electronic devices made according tothe methods of the present disclosure. The examples are merelyillustrative and are not intended to limit the present disclosure withregard to the materials, conditions, or process parameters set forththerein. All parts are percentages by weight unless otherwise indicated.

EXAMPLES Example 1

A semiconducting polymer, PQT-12, poly(3,3′″-didodecylquaterthiophene),corresponding to Formula (II) where R≡C₁₂H₂₅, is used with commerciallyexpandable graphite (160-50-N GRAFGUARD, available from GrafTech,Cleveland, Ohio) in this example. The graphite is first briefly heatedto 1000° C. in forming gas of 3% hydrogen in argon for 60 seconds. Theresulting exfoliated graphite is dispersed in a solution of PQT-12 in1,2-dichlorobenzene by sonication for 30 minutes to form a homogeneoussuspension. The graphene is from about 0.05 to 1.0 volume percent of thePQT-12. The suspension is filtered with a 1.0 μm glass filter and readyfor depositing.

OTFTs using the above PQT/graphene composite are fabricated using theprocedure disclosed in J. Am. Chem. Soc., 2004, 126, pp. 3378-3379.

Example 2

Graphite oxide is synthesized from natural graphite by a modifiedHummers method described in Chem. Mater., 1999, 11, pp. 771-778. Thesynthesized graphite oxide is suspended in water to give a browndispersion, which is subjected to dialysis to completely remove residualsalts and acids. The purified graphite oxide is re-dispersed inultrapure water. Exfoliation of graphite oxide to graphene oxide isachieved by sonication for 30 minutes. The homogenous dispersion ismixed with hydrazine solution and ammonia solution in a glass bottle.The mixture is heated to 95° C. for 1 hour to chemically convertgraphene oxide to graphene.

A surfactant,1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethyleneglycol)-5000]is added to the dispersion. The graphene is centrifuged, collected, andredispersed in DMF. After repeating re-suspension and centrifugationseveral times in DMF to remove the surfactant, the aggregates arere-dispersed in 1,2-dichlorobenzene. PQT-12 semiconducting polymer isadded to form a composite for OTFT fabrication.

The devices of the present disclosure have been described with referenceto exemplary embodiments. Obviously, modifications and alterations willoccur to others upon reading and understanding the preceding detaileddescription. It is intended that the exemplary embodiment be construedas including all such modifications and alterations insofar as they comewithin the scope of the appended claims or the equivalents thereof.

1. An electronic device comprising a semiconducting layer; thesemiconducting layer comprising (i) an organic semiconductor and (ii)graphene.
 2. The electronic device of claim 1, wherein the organicsemiconductor and the graphene are stratified with respect to eachother.
 3. The electronic device of claim 1, wherein the organicsemiconductor and graphene are layered structures in the semiconductinglayer.
 4. The electronic device of claim 1, wherein the graphene isdispersed substantially throughout the semiconducting layer.
 5. Theelectronic device of claim 1, wherein the graphene is chemicallymodified.
 6. The electronic device of claim 5, wherein the graphene ismodified with a conjugated group selected from the group consisting ofthiophene-based oligomers and polymers, pyrenes, phthalocyanines,polyphenylvinylidenes, polyfluorenes, polycarbazoles,polyindolocarbazoles, polytriarylamines, and polyphenylenes.
 7. Theelectronic device of claim 1, wherein the organic semiconductorcomprises a semiconducting polymer of Formula (I):

wherein A is a divalent linkage; each R is independently selected fromhydrogen, alkyl or substituted alkyl, aryl or substituted aryl, alkoxyor substituted alkoxy, a heteroatom-containing group, or halogen; and nis from 2 to about 5,000.
 8. The electronic device of claim 7, whereinthe divalent linkage is selected from

and combinations thereof, wherein each R′ is independently selected fromhydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,halogen, —CN, or —NO₂.
 9. The electronic device of claim 1, wherein theorganic semiconductor is a polythiophene of Formula (II), (III), (IV),(V), (VI), (VII), or (VIII):

wherein each R, R′, and R₁ is independently selected from hydrogen,alkyl or substituted alkyl, aryl or substituted aryl, alkoxy orsubstituted alkoxy, a heteroatom-containing group, or halogen; and n isfrom 2 to about 5,000.
 10. The electronic device of claim 1, wherein thegraphene has functional sites.
 11. The electronic device of claim 10,wherein the functional sites comprise carbonyl groups, carboxylic acidgroups, epoxide groups, or hydroxyl groups.
 12. The electronic device ofclaim 1, wherein the semiconducting layer comprises from about 0.001 toabout 10 percent by weight of the graphene.
 13. The electronic device ofclaim 1, wherein the semiconductor layer comprising from about 0.01 toabout 5 percent by weight of the graphene.
 14. The electronic device ofclaim 1, wherein the graphene is a layer formed by depositing graphiteoxide and reducing the graphite oxide to form a graphene layer.
 15. Theelectronic device of claim 1, wherein the semiconducting layer is madeby a process comprising: dispersing graphite oxide in an aqueoussolution comprising water and ammonia; converting the graphite oxide tographene; dispersing the aqueous solution in an aprotic solvent andneutralizing any static charge; dispersing the graphene in an organicsolvent to form a graphene dispersion; mixing the graphene dispersionwith an organic semiconductor to form a mixture; and depositing themixture on a surface of a substrate to form the semiconducting layer.16. The electronic device of claim 1, wherein the semiconducting layeris formed by a process comprising: forming a homogeneous suspension ofthe organic semiconductor and graphene oxide; depositing the suspensionon a surface; and converting the graphene oxide to graphene.
 17. Anelectronic device comprising a semiconducting layer; the semiconductinglayer comprising at least a first layer and a second layer; the firstlayer comprising an organic semiconductor; and the second layercomprising graphene.
 18. The electronic device of claim 17, wherein theorganic semiconductor comprises a majority of the first layer, and thegraphene comprises a majority of the second layer.
 19. The electronicdevice of claim 17, wherein the second layer is formed by the reductionof graphite oxide.
 20. The electronic device of claim 17, wherein theorganic semiconductor is a polythiophene of Formula (II):

wherein R is alkyl; and n is from 2 to about 5,000.
 21. A thin-filmtransistor comprising a semiconducting layer, the semiconducting layercomprising an organic semiconductor and graphene.
 22. The thin-filmtransistor of claim 21, wherein the graphene forms a percolation networkwithin the semiconducting layer.
 23. The thin-film transistor of claim21, wherein the graphene concentration in the semiconducting layer islower than the critical concentration for a percolation network.
 24. Thethin-film transistor of claim 21, wherein the organic semiconductor andgraphene are stratified with respect to each other.
 25. A process forforming a semiconducting layer on a substrate, comprising stratifying atleast one organic semiconductor with at least one graphene.
 26. Theprocess of claim 25, wherein the graphene is a layer formed bydepositing graphite oxide and reducing the graphite oxide to form thegraphene layer.
 27. The process of claim 25, wherein the semiconductinglayer is formed by: dispersing graphite oxide in an aqueous solutioncomprising water and ammonia; converting the graphite oxide to graphene;dispersing the aqueous solution in an aprotic solvent and neutralizingany static charge; dispersing the graphene in an organic solvent to forma graphene dispersion; mixing the graphene dispersion with an organicsemiconductor to form a mixture; and depositing the mixture upon thesubstrate.
 28. The process of claim 25, wherein the semiconducting layeris formed by: forming a homogeneous suspension of the organicsemiconductor and graphene oxide; depositing the suspension on a surfaceof the substrate; and converting the graphene oxide to graphene.